CN102358770A - Copolymer coating with moisture self-repair function and preparation method - Google Patents
Copolymer coating with moisture self-repair function and preparation method Download PDFInfo
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- CN102358770A CN102358770A CN2011102152221A CN201110215222A CN102358770A CN 102358770 A CN102358770 A CN 102358770A CN 2011102152221 A CN2011102152221 A CN 2011102152221A CN 201110215222 A CN201110215222 A CN 201110215222A CN 102358770 A CN102358770 A CN 102358770A
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Abstract
The invention relates to a copolymer coating with a moisture self-repair function, and the coating is formed by copolymerization of isocyanate group-containing monomers and fluorinated acrylate monomers. The preparation method comprises the steps of: preparing isocyanate end group-containing functional monomers with diisocyanate, dihydric alcohol and hydroxyl-containing monomers as the raw materials, then subjecting the functional monomers to copolymerization with fluorine containing acrylic acid ester, a cross-linking agent and a photosensitizer under ultraviolet light initiation, thus obtaining a copolymer coating containing isocyanate monomers and fluorinated acrylate. The copolymer of the invention can be used as a protection coating of metallic and decoration materials, and the coating in the invention is not affected by ambient moisture. When the coating is damaged, a crack on the coating can be repaired on its own with the aid of ambient moisture. When the coating is damaged, a crack on the coating can be repaired on its own with the aid of ambient moisture, so that the original protection role of the coating is regained, the service life of the coating is extended, and the loss is reduced. The preparation method of the copolymer has the advantages of simple process, low cost, and easy implementation, and is suitable for large scale popularization and application.
Description
Technical field
The invention belongs to coated material with polymkeric substance and preparation method thereof, particularly a kind of copolymer coated and preparation method with moisture self-repair function.
Background technology
In current global range, annual because the financial loss that the corrosive attack of metal (iron, aluminium etc.) causes is very huge, therefore, solve the erosion-resisting problem of metal is an important field of research always.Metal Protection method commonly used forms one deck inert resist through methods such as coating, plating on its surface exactly and realizes.Mostly coating generally is polymer materials, and polymer materials sustains damage under external force easily, destroys with the form of crackle, and can expand increase gradually, causes further infringement, thereby badly influences the performance of polymer materials.And crackle is very difficult to detect and control, makes the application of polymer materials receive influence to a certain degree, because; In case coating receives external influence and destroys; The metal of substrate also can come out so, receives the erosion of external environment, thereby brings bigger financial loss.
Summary of the invention
The objective of the invention is to above-mentioned existing problems; Provide a kind of multipolymer as coated material with moisture self-repair function; This coating does not receive the influence of ambient moisture under normal environment for use, and when coating sustained damage, coating crack can be repaired by the moisture in the environment voluntarily.
Technical scheme of the present invention:
A kind of have the copolymer coated of moisture self-repair function; Formed by monomer that contains isocyanate groups and fluorinated acrylate monomer copolymerization, the said monomer that contains isocyanate groups is the monomer based on tolylene diisocyanate, Tri Ethyleneglycol and Rocryl 400; Monomer based on dimethylmethane vulcabond, Macrogol 200 and Rocryl 400; Monomer based on isophorone diisocyanate, Liquid Macrogol and NMA; Monomer based on hexamethylene diisocyanate, Polyethylene Glycol-600 and Rocryl 400; Monomer based on isophorone diisocyanate, Tri Ethyleneglycol and Rocryl 400; Said fluorinated acrylate monomer is vinylformic acid trifluoro methyl esters, vinylformic acid hexafluoro butyl ester, methylacrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate or methylacrylic acid ten difluoro heptyl esters.
A kind of copolymer coated preparation method with moisture self-repair function, step is following:
1) contains the monomeric preparation of isocyanate groups: under nitrogen protection, vulcabond is mixed with Benzoyl chloride 99min., stir and carry out oil bath down and heat; When temperature reaches 65 ℃, add divalent alcohol, and continue reaction 2h down, make ending isocyanate prepolymer at 65 ℃; Prepared ending isocyanate prepolymer is dissolved with THF; Add the function monomer that contains two keys then, nitrogen protection is stirred down and is reacted 4h at 40 ℃, makes to contain isocyanate-monomer;
2) copolymer coated preparation; After will containing the monomer of isocyanic ester, fluorine-containing (methyl) acrylate monomer, linking agent and photosensitizers mixing, on sheet metal, film, utilize UV-light to cause then through the copolyreaction film forming;
3) anneal; The exsiccant film takes out, puts into baking oven, and at 120 ℃ of following anneal 10min, cooling gets final product at normal temperatures then.
Said vulcabond is tolylene diisocyanate (TDI), dimethylmethane vulcabond (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) or dicyclohexyl methane diisocyanate (HMDI); Said divalent alcohol comprises that molecular weight is any one ethers and the ester class divalent alcohol of 100-1000.
The mol ratio of said vulcabond, Benzoyl chloride 99min. and divalent alcohol is 4:0.01:1.
The said function monomer that contains two keys is Rocryl 400 or N hydroxymethyl acrylamide.
The volume ratio of said ending isocyanate prepolymer and THF is 1:2; The amount ratio of ending isocyanate prepolymer and the function monomer that contains two keys is that the mol ratio of isocyano and hydroxyl is 2:1.
Said linking agent is ethylene glycol dimethacrylate (EDGMA) or trimethylol propane trimethyl methyl acrylate (TRIM).
Said photosensitizers is the mixture of one or both arbitrary proportions in 2-hydroxy-2-methyl-1-phenyl-acetone (1173), 1-hydroxy-cyclohexyl phenyl ketone (184) and 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone (907).
Said monomer and the monomeric mass ratio of acrylate containing fluorine that contains isocyanic ester is 7:3 to 5:5; The consumption of linking agent is the 5-10% of copolyreaction monomer total mass; The consumption of photosensitizers is the 2-4% of copolyreaction monomer total mass.
Principle of work of the present invention:
This multipolymer is formed with other a kind of (methyl) acrylic ester monomer copolymerization that includes the hydrophobic fluorine group by a kind of monomer that includes active terminal isocyanate groups.Isocyanic ester is very responsive to water, is exposed to be easy in the air and airborne reaction of moisture, and two molecule isocyanate can be reacted with a part water, generate urea.This reaction process is shown in chemical equation 1 and 2.Wherein isocyano elder generation generates the carboxylamine midbody with water, and carboxylamine decomposes rapidly then, generates amido and carbonic acid gas, and the amido ability is rapid and another isocyano reaction generates urea.This series reaction makes the reparation of matrix under the moisture environment that contains isocyanate reactive group become possibility.
On the other hand,, can improve the film forming hydrophobicity of polymkeric substance preferably, make the water-intake rate of polymeric film reduce greatly, can play the effect of isocyanate groups in the good protection polymeric coating through in polymkeric substance, introducing fluorine-containing groups.Simultaneously, in the process of multipolymer coating, fluorine-containing groups is because its low surface free energy more easily in the solid-air interface enrichment, forms good aqueous vapor sealing coat, makes that isocyanate groups can conductively-closed, avoids the effect of aqueous vapor; And isocyanate groups has strong polarity, more is prone in the enrichment of polar group surface, forms repair layer.So, when this coating was damaged, surperficial fluorine sealing coat was opened, and made inner isocyanate groups come out.At this moment, coupled reaction can take place in the isocyanate groups on slight crack both sides under the effect of water in air gas, and two molecule isocyanate groups and a part water form urea, thereby reaches the effect of reparation.
Advantage of the present invention is: this multipolymer can be used as metal and finishing material protective coating; This coating does not receive the influence of ambient moisture under normal environment for use; And when coating sustained damage, coating crack can be repaired by the moisture in the environment voluntarily, recovered original provide protection; Thereby can prolong coating work-ing life, reduce the loss.Preparing method's technology of this multipolymer is simple, cost is low, easy to implement, be suitable for large-scale promotion application.
Description of drawings
Contrast photo before and after accompanying drawing 1 embodiment 1 sample is repaired.
Contrast photo before and after accompanying drawing 2 embodiment 2 samples are repaired.
Contrast photo before and after accompanying drawing 3 embodiment 3 samples are repaired.
Embodiment
Embodiment 1:
A kind of copolymer coated preparation method with moisture self-repair function, step is following:
1) get 80mmol TDI and the 0.44ml Benzoyl chloride 99min. mixes, temperature is set to 65 ℃, gets 20mmol Tri Ethyleneglycol (TEG) again, is added drop-wise in the reactor drum, regulates and drips speed, and TEG was dripped off in 30 minutes, reacts 2h again.Then, reaction product in the normal hexane solvent, was left standstill several hours; Pour out supernatant, revolve steaming, pour out supernatant after leaving standstill afterwards with being added to again in the mixed solvent (v/v=3/1) of normal hexane and ETHYLE ACETATE after the dissolving of 20mL THF; Revolve steaming, vacuum-drying obtains ending isocyanate prepolymer.
2) ending isocyanate prepolymer and the Rocryl 400 with above-mentioned preparation reacts with mol ratio-NCO:-OH=2:1, and preparing end group is the methyl acrylic ester monomer of isocyanic ester.Get 10ml THF dissolving, under nitrogen protection, join in the there-necked flask.Stir with magnetic stirrer then, Heating temperature is set to 40 ℃, gets 10 gram Rocryl 400s and joins in the there-necked flask and react.The rate of addition of regulating Rocryl 400 dripped off about 30 minutes.React 4h down at 40 ℃ again.Afterwards, reaction gained mixture is added in the mixed solvent (v/v=3/1) of 300mL normal hexane and ETHYLE ACETATE, left standstill several hours; Pour out supernatant, revolve steaming, repeat to precipitate twice afterwards with being added drop-wise to again in the mixed solvent (vol:vol=1:1) of normal hexane and ETHYLE ACETATE after the THF dissolving; Revolve steaming; Product is collected in vacuum-drying, and cryopreservation is subsequent use.
3) copolymer coated preparation; The methylacrylic acid hexafluoro butyl ester that takes by weighing 3 grams mixes with mol ratio 3:7 with the function monomer that contains isocyanic ester of above-mentioned preparation; 5.0% the linking agent trimethylol propane trimethyl methyl acrylate (TRIM) that will account for the monomer total mass again joins in the there-necked flask; Photosensitizers 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) the phenyl]-1-acetone (907) that will account for total monomer quality 2.0% simultaneously joins in the reaction flask; Mix with electromagnetism; After spin-coating film on the aluminium flake of treated mistake, put into the UV reactive device, under 1000 watts of power, react 2 minutes film forming.
The treatment process of said aluminium flake is: aluminium flake is cut to 2cm * 4cm size, removes the top layer zone of oxidation with sand papering earlier, clean 10min with Virahol and acetone mixed solvent then and deoil; Use twice of washed with de-ionized water again; Ultrasonic deionized water immersion treatment 10min down pulls N out
2Under dry subsequent use.
4) anneal; The exsiccant film takes out, puts into baking oven, and at 120 ℃ of following anneal 10min, cooling gets final product at normal temperatures then.
This copolymer coated Performance Detection:
1) slight crack is handled: with the blade vestige of on the aluminium flake of coating, crossing, make slight crack;
2) repairing test: the sample that will prepare slight crack is put into the container of the sealing of a fixed temperature and humidity.Design temperature T=30 ℃, humidity RH=95% handles sample 12h with this understanding.The comparative test result picture is as shown in Figure 1 before and after being coated with film healing, and visible coating crack can be repaired by the moisture in the environment voluntarily, thereby recovers original provide protection.
Embodiment 2:
A kind of copolymer coated preparation method with moisture self-repair function, step is following:
1) get 80mmol MDI and the 0.44ml Benzoyl chloride 99min. mixes, temperature is set to 65 ℃, gets the 20mmol Macrogol 200 again, is added drop-wise in the reactor drum, regulates and drips speed, and Macrogol 200 was dripped off in 30 minutes, reacts 2h again.Then, reaction product in the normal hexane solvent, was left standstill several hours; Pour out supernatant, revolve steaming, pour out supernatant after leaving standstill afterwards with being added to again in the mixed solvent (v/v=3/1) of normal hexane and ETHYLE ACETATE after the dissolving of 20mL THF; Revolve steaming; Vacuum-drying obtains product, ending isocyanate prepolymer.
2) above-mentioned ending isocyanate prepolymer and Rocryl 400 are reacted with mol ratio-NCO:-OH=2:1, preparing end group is the methyl acrylic ester monomer of isocyanic ester.Get 10ml THF dissolving ending isocyanate prepolymer, under nitrogen protection, join in the there-necked flask.Stir with certain speed with magnetic stirrer then, Heating temperature is set to 40 ℃, gets 10 gram HEMA and joins in the there-necked flask and react.Regulate the rate of addition of Rocryl 400, make it about 30 minutes, to drip off.React 4h down at 40 ℃ again.Afterwards, reaction gained mixture is added in the mixed solvent (v/v=3/1) of 300mL normal hexane and ETHYLE ACETATE, left standstill several hours; Pour out supernatant, revolve steaming, repeat to precipitate twice afterwards with being added drop-wise to again in the mixed solvent (vol:vol=1:1) of normal hexane and ETHYLE ACETATE after the THF dissolving; Revolve steaming; Product is collected in vacuum-drying, and cryopreservation is subsequent use.
3) copolymer coated preparation; Claim that 2 gram methylacrylic acids, ten difluoro heptyl esters mix with mol ratio 3:7 with the monomer that contains isocyanic ester of above-mentioned preparation; The linking agent ethylene glycol dimethacrylate (EDGMA) that will account for total monomer quality 10.0% again joins in the there-necked flask; The photosensitizers 2-hydroxy-2-methyl-1-phenyl-acetone (1173) that will account for monomer total mass 3.0% simultaneously joins in the reaction flask; Mix with electromagnetism, after spin-coating film on the aluminium flake of treated mistake, put into the UV reactive device, under 1000 watts of power; Reacted film forming 2 minutes.
The treatment process of said aluminium flake is identical with embodiment 1.
4) annealing conditions: the aluminium flake that above-mentioned UV-light reaction is become is filmed, put into baking oven, at 120 ℃ of following anneal 10min, cooling gets final product at normal temperatures then.
This copolymer coated Performance Detection:
1) slight crack is handled: with the blade vestige of on the aluminium flake of coating, crossing, make slight crack.
2) repairing test: the sample that will prepare slight crack is put into the container of the sealing of a fixed temperature and humidity.Design temperature T=30 ℃, humidity RH=95% handles sample 12h with this understanding.The comparative test result picture is as shown in Figure 2 before and after being coated with film healing, and visible coating crack can be repaired by the moisture in the environment voluntarily, thereby recovers original provide protection.
Embodiment 3:
A kind of copolymer coated preparation method with moisture self-repair function, step is following:
1) get 80mmol IPDI and the 0.44ml Benzoyl chloride 99min. mixes, temperature is set to 65 ℃, gets the 20mmol Liquid Macrogol again, is added drop-wise in the reactor drum, regulates and drips speed, and Liquid Macrogol was dripped off in 30 minutes, reacts 2h again.Then, reaction product in the normal hexane solvent, was left standstill several hours; Pour out supernatant, revolve steaming, pour out supernatant after leaving standstill afterwards with being added to again in the mixed solvent (v/v=3/1) of normal hexane and ETHYLE ACETATE after the dissolving of 20mL THF; Revolve steaming; Vacuum-drying obtains product, ending isocyanate prepolymer.
2) ending isocyanate prepolymer and the N hydroxymethyl acrylamide with above-mentioned preparation reacts with mol ratio-NCO:-OH=2:1, prepares the methyl acrylamide monomer that end group is an isocyanic ester.Get 10ml THF dissolving, under nitrogen protection, join in the there-necked flask.Stir with certain speed with magnetic stirrer then, Heating temperature is set to 40 ℃, gets 10 gram N hydroxymethyl acrylamides and joins 40 ℃ of following reaction 4h in the there-necked flask.Afterwards, be added in the mixed solvent (v/v=3/1) of 300mL normal hexane and ETHYLE ACETATE, left standstill several hours filling reaction gained mixture; Pour out supernatant, revolve steaming, repeat to precipitate twice afterwards with being added drop-wise to again in the mixed solvent (vol:vol=1:1) of normal hexane and ETHYLE ACETATE after the THF dissolving; Revolve steaming; Product is collected in vacuum-drying, and cryopreservation is subsequent use.
3) copolymer coated preparation; Taking by weighing 4 gram vinylformic acid trifluoro methyl esters mixes with mol ratio 5:5 with the monomer that contains isocyanic ester of as above preparation; The linking agent ethylene glycol dimethacrylate (EDGMA) that will account for total monomer quality 10.0% again joins in the there-necked flask; The photosensitizers 1-hydroxy-cyclohexyl phenyl ketone (184) that will account for monomer total mass 2.5% simultaneously simultaneously joins in the reaction flask; Mix with electromagnetism, after spin-coating film on the aluminium flake of treated mistake, put into the UV reactive device, under 1000 watts of power; Reacted film forming 2 minutes.
The treatment process of said aluminium flake is identical with embodiment 1.
4) annealing conditions: the aluminium flake that above-mentioned UV-light reaction is become is filmed, put into baking oven, at 120 ℃ of following anneal 10min, cooling gets final product at normal temperatures then.
This copolymer coated Performance Detection:
1) slight crack is handled: with the blade vestige of on the aluminium flake of coating, crossing, make slight crack.
2) repairing test: the sample that will prepare slight crack is put into the container of the sealing of a fixed temperature and humidity.Design temperature T=30 ℃, humidity RH=95% handles sample 12h with this understanding.The comparative test result picture is as shown in Figure 3 before and after being coated with film healing, and visible coating crack can be repaired by the moisture in the environment voluntarily, thereby recovers original provide protection.
Claims (9)
1. one kind has the copolymer coated of moisture self-repair function; It is characterized in that: formed by monomer that contains isocyanate groups and fluorinated acrylate monomer copolymerization, the said monomer that contains isocyanate groups is the monomer based on tolylene diisocyanate, Tri Ethyleneglycol and Rocryl 400; Monomer based on dimethylmethane vulcabond, Macrogol 200 and Rocryl 400; Monomer based on isophorone diisocyanate, Liquid Macrogol and NMA; Monomer based on hexamethylene diisocyanate, Polyethylene Glycol-600 and Rocryl 400; Monomer based on isophorone diisocyanate, Tri Ethyleneglycol and Rocryl 400; Said fluorinated acrylate monomer is vinylformic acid trifluoro methyl esters, vinylformic acid hexafluoro butyl ester, methylacrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate or methylacrylic acid ten difluoro heptyl esters.
2. copolymer coated preparation method who has the moisture self-repair function according to claim 1 is characterized in that step is following:
1) contains the monomeric preparation of isocyanate groups: under nitrogen protection, vulcabond is mixed with Benzoyl chloride 99min., stir and carry out oil bath down and heat; When temperature reaches 65 ℃, add divalent alcohol, and continue reaction 2h down, make ending isocyanate prepolymer at 65 ℃; Prepared ending isocyanate prepolymer is dissolved with THF; Add the function monomer that contains two keys then, nitrogen protection is stirred down and is reacted 4h at 40 ℃, makes to contain isocyanate-monomer;
2) copolymer coated preparation; After will containing the monomer of isocyanic ester, fluorine-containing (methyl) acrylate monomer, linking agent and photosensitizers mixing, on sheet metal, film, utilize UV-light to cause then through the copolyreaction film forming;
3) anneal; The exsiccant film takes out, puts into baking oven, and at 120 ℃ of following anneal 10min, cooling gets final product at normal temperatures then.
3. according to the said copolymer coated preparation method with moisture self-repair function of claim 2, it is characterized in that: said vulcabond is tolylene diisocyanate (TDI), dimethylmethane vulcabond (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) or dicyclohexyl methane diisocyanate (HMDI); Said divalent alcohol comprises that molecular weight is any one ethers and the ester class divalent alcohol of 100-1000.
4. according to the said copolymer coated preparation method with moisture self-repair function of claim 2, it is characterized in that: the mol ratio of said vulcabond, Benzoyl chloride 99min. and divalent alcohol is 4:0.01:1.
5. according to the said copolymer coated preparation method with moisture self-repair function of claim 2, it is characterized in that: the said function monomer that contains two keys is Rocryl 400 or N hydroxymethyl acrylamide.
6. according to the said copolymer coated preparation method with moisture self-repair function of claim 2, it is characterized in that: the volume ratio of said ending isocyanate prepolymer and THF is 1:2; The amount ratio of ending isocyanate prepolymer and the function monomer that contains two keys is that the mol ratio of isocyano and hydroxyl is 2:1.
7. according to the said copolymer coated preparation method with moisture self-repair function of claim 2, it is characterized in that: said linking agent is ethylene glycol dimethacrylate (EDGMA) or trimethylol propane trimethyl methyl acrylate (TRIM).
8. according to the said copolymer coated preparation method with moisture self-repair function of claim 2, it is characterized in that: said photosensitizers is the mixture of one or both arbitrary proportions in 2-hydroxy-2-methyl-1-phenyl-acetone (1173), 1-hydroxy-cyclohexyl phenyl ketone (184) and 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone (907).
9. according to the said copolymer coated preparation method with moisture self-repair function of claim 2, it is characterized in that: said monomer and the monomeric mass ratio of acrylate containing fluorine that contains isocyanic ester is 7:3 to 5:5; The consumption of linking agent is the 5-10% of copolyreaction monomer total mass; The consumption of photosensitizers is the 2-4% of copolyreaction monomer total mass.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669932A (en) * | 2016-01-13 | 2016-06-15 | 中山大学 | Photic self-repairing cross-linked polymer and preparation method and application thereof |
| CN106394572A (en) * | 2016-10-21 | 2017-02-15 | 苏州大成电子科技有限公司 | Wear-resisting panoramic train carriage |
| CN109735194A (en) * | 2019-01-16 | 2019-05-10 | 常熟理工学院 | Ultraviolet light solidifies scratch resistance selfreparing TPU stealth film and preparation method thereof |
| CN110621707A (en) * | 2017-04-13 | 2019-12-27 | 株式会社世可 | Self-repairing functional polyethylene compound and preparation method thereof |
| CN115746602A (en) * | 2022-11-12 | 2023-03-07 | 烟台德邦科技股份有限公司 | High-reliability UV protective coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040900A (en) * | 2010-11-11 | 2011-05-04 | 常州大学 | Fluorocoating resin and preparation method thereof |
-
2011
- 2011-07-29 CN CN 201110215222 patent/CN102358770B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040900A (en) * | 2010-11-11 | 2011-05-04 | 常州大学 | Fluorocoating resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| BAGHDACHI, J., ET AL.: "Design and Development of Self - Healing polymers and coatings", 《ACS SYMPOSIUM SERIES》 * |
| 安秋凤等: "氟代聚丙烯酸酯改性聚氨酯复合乳液的制备及其疏水性", 《日用化学工业》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669932A (en) * | 2016-01-13 | 2016-06-15 | 中山大学 | Photic self-repairing cross-linked polymer and preparation method and application thereof |
| CN105669932B (en) * | 2016-01-13 | 2018-05-11 | 中山大学 | A kind of smooth self-repairing cross-linked polymer and its preparation method and application |
| CN106394572A (en) * | 2016-10-21 | 2017-02-15 | 苏州大成电子科技有限公司 | Wear-resisting panoramic train carriage |
| CN110621707A (en) * | 2017-04-13 | 2019-12-27 | 株式会社世可 | Self-repairing functional polyethylene compound and preparation method thereof |
| CN110621707B (en) * | 2017-04-13 | 2021-11-02 | 株式会社世可 | Self-repairing functional polyethylene compound and preparation method thereof |
| CN109735194A (en) * | 2019-01-16 | 2019-05-10 | 常熟理工学院 | Ultraviolet light solidifies scratch resistance selfreparing TPU stealth film and preparation method thereof |
| CN115746602A (en) * | 2022-11-12 | 2023-03-07 | 烟台德邦科技股份有限公司 | High-reliability UV protective coating and preparation method thereof |
| CN115746602B (en) * | 2022-11-12 | 2023-12-01 | 烟台德邦科技股份有限公司 | High-reliability UV protective coating and preparation method thereof |
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